Syntheses and structures of one CuI-containing coordination polymer and two macrocyclic supramolecular complexes based on flexible 1,3,4-oxadiazole-containing ligands.

Three coordination complexes with Cu(I) centres have been prepared using the symmetrical flexible organic ligands 1,3-bis{[5-(quinolin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}propane (L1) and 1,4-bis{[5-(quinolin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}butane (L2). Crystallization of L1 with Cu(SO3CF3)2 and of L2 with Cu(BF4)2 and Cu(ClO4)2 in a CH2Cl2/CH3OH mixed-solvent system at room temperature afforded the coordination complexes catena-poly[[copper(I)-μ-1,3-bis{[5-(quinolin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}propane] methanesulfonate dichloromethane 0.6-solvate], {Cu(C25H18N6O2S2)·0.6CH2Cl2}n, (I), bis(μ-1,4-bis{[5-(quinolin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}butane)dicopper(I) bis(tetrafluoridoborate)-dichloromethane-methanol (1/1.5/1), Cu2(C26H20N6O2S2)22·1.5CH2Cl2·CH3OH, (II), and bis(μ-1,4-bis{[5-(quinolin-2-yl)-1,3,4-oxadiazol-2-yl]sulfanyl}butane)dicopper(I) bis(perchlorate)-dichloromethane-methanol (1/2/1), Cu2(C26H20N6O2S2)22·2CH2Cl2·CH3OH, (III). Under the control of the dumbbell-shaped CF3SO3(-) anion, complex (I) forms a one-dimensional chain and neighbouring chains form a spiral double chain. Under the control of the regular tetrahedron-shaped BF4(-) and ClO4(-) anions, complexes (II) and (III) have been obtained as bimetallic rings, which further interact via π-π interactions to form two-dimensional networks. The anions play a decisive role in determining the arrangement of these discrete molecular complexes in the solid state.